KR101509146B1 - Dibenzylamine hydrophobe - Google Patents

Abstract

상기 식에서, 각 R¹은 독립적으로 메틸 또는 에틸이고; n은 1 내지 10이다. 본 발명의 화합물은 코팅 제제용 유동성 조절제로서 유용한, 소수성으로 개질된 알킬렌 옥사이드 우레탄 중합체 제조에 유용하다.The present invention relates to compounds characterized by the formula:

Wherein each R < ¹ > is independently methyl or ethyl; n is 1 to 10; The compounds of the present invention are useful in the preparation of hydrophobically modified alkylene oxide urethane polymers useful as flow control agents for coating formulations.

Description

Dibenzylamine Fractional Component {DIBENZYLAMINE HYDROPHOBE}

The present invention relates to amine-based hydrophobic components useful in preparing hydrophobically modified alkylene oxide urethane polymers useful as flow control agents for coating formulations.

Flow modifiers are typically designed to impart desirable rheological properties to the coating formulation over a wide range of shear rates. U.S. Patent No. 7,741,402 discloses an ethylene oxide urethane polymer (amine-modified HEUR) modified with a minor component containing an organic base, for example, a secondary or tertiary amine, trigger to provide viscosity control. If the pH of the HEUR composition is low enough for the pK _a of the contained base, the proton is added to the basic group and the viscosity is relatively low; When the pH is high enough, an associated increase in viscosity occurs. Thus, when a basic hydrophobic component is included in a HEUR polymer, a relatively high concentration of the polymer is soluble in water at low pH; Once the solution is added to the high pH environment of the paint coating, the base is deprotonated and the associated viscosity increasing mechanism is activated.

The amine-modified HEUR may be sensitive to the pH of the paint formulation to which it is added. For example, the time and heat aging can reduce the pH of the formulation to a level below the critical pH that is conductive to the associated viscosity increase, thereby resulting in a more inferior formulation; As a result, it would be desirable to find hydrophobic components, more particularly amine-based hydrophobic components, that preserve the desired viscosity of the formulation in the face of the pH-lowering mechanism.

In one aspect, the present invention meets this need by providing a compound characterized by the formula:

In this formula,

Each R < ¹ > is independently methyl or ethyl;

n is 1 to 10;

In a second aspect, the invention relates to a composition comprising a stable aqueous dispersion of an alkylene oxide urethane polymer modified hydrophobically by an endcapping tertiary amine group, characterized by the structure:

Wherein each R < ¹ > and n is as defined above.

The polymers of the present invention are useful as flow control agents for paint formulations formulated at a wide range of pH.

In a first aspect, the invention relates to a compound characterized by the formula (I)

Wherein R ¹ and n are as defined above. Preferably, R < ¹ > is ethyl and n is preferably 3 to 5.

The compounds of the present invention can be obtained according to the following reaction scheme:

In a second aspect, the present invention relates to a composition comprising a stable aqueous dispersion of an alkylene oxide urethane polymer which is hydrophobically modified by a terminal capped tertiary amine group, characterized by the following structure Ia:

Wherein R ¹ and n are as defined above. R ¹ is preferably ethyl, and n is preferably in the range of usually from 3 to 6.

The hydrophobically modified alkylene oxide urethane polymer comprises a) a compound of formula (I); b) diisocyanate; And c) water-soluble polyalkylene glycols together.

The diisocyanate starting material is a C ₄ -C ₂₀ aliphatic or aromatic diisocyanate. As used herein, "aliphatic" refers to a saturated or partially unsaturated linear-, branched-, or cycloaliphatic, or combination thereof. Examples of suitable diisocyanates include 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-diisocyanatohexane, 1,10-decamethylene diisocyanate , 4,4'-methylenebis (isocyanatocyclohexane), 1,4-cyclohexylene diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclo Hexene, m- and p -phenylene diisocyanate, 2,6- and 2,4-toluene diisocyanate, xylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, Diisocyanate, 4,4'-methylene diphenyl isocyanate, 1,5-naphthylene diisocyanate, and 1,5-tetrahydronaphthylene diisocyanate.

Water-soluble polyalkylene glycols refer to water-soluble polyethylene oxide, water-soluble polyethylene oxide / polypropylene oxide copolymer, and water-soluble polyethylene oxide / polybutylene oxide copolymer. As used herein, the term propylene oxide refers to any of the polymers having - (OCH ₂ CH ₂ CH ₂ ) - and / or - (OCH (CH ₃ ) CH ₂ ) - repeats.

Preferred water soluble polyalkylene oxides have a weight average molecular weight in the range of polyethylene glycol, in particular in the range of not less than 4000 daltons, more preferably not less than 6000 daltons, most preferably not less than 7,000 to 20,000 daltons, more preferably not more than 12,000 daltons and most preferably not more than 9,000 daltons Polyethylene glycol. An example of a suitable polyethylene glycol is PEG 8000, which is commercially available as CARBOWAX ^TM 8000 polyethylene glycol (a trademark of the Dow Chemical Company ("Dow") of Midland, MI or the affiliated companies of the Dow).

Alternatively, the water soluble polyalkylene oxide may be combined with a polyfunctional group other than the polyisocyanate to form a non-urethane composition which may benefit from tertiary amine-modification as described herein. Examples of suitable alternative linking groups include epihalohydrins, gemdihalides, and aminoplasts.

The compositions of the present invention are useful in coating formulations, especially paint formulations, and can include any or all of the following: solvent; Filler; Pigments such as titanium dioxide, mica, calcium carbonate, silica, zinc oxide, ground glass, aluminum trihydrate, talc, antimony trioxide, fly ash and clay; Polymer-encapsulated or partially encapsulated opacifying pigment particles, including polymer encapsulated pigments, for example, titanium dioxide, zinc oxide or lithopone polymers; A polymer or polymer emulsion that adsorbs or binds to the pigment surface, such as titanium dioxide; A hollow pigment comprising a pigment having at least one void; Dispersing agents such as amino alcohols and polycarboxylates; Surfactants; Defoamer; Preservatives, for example, biocides, fungicides, fungicides, fungicides and combinations thereof; A flow agent; A leveling agent; And further neutralizing agents such as hydroxides, amines, ammonia and carbonates.

For example, the coating formulation may comprise i) opaque pigment particles having a diameter in the range of 100 nm to 500 nm and an index of refraction of at least 1.8, for example titanium dioxide particles; ii) an encapsulating polymer, and iii) a polymeric-dispersed encapsulated opacifying pigment particle and a polymeric dispersant for the polymer. Such polymer-encapsulated opacifying pigment particles are described, for example, in U.S. Patent Publication No. 2010/0298483 Al. In another embodiment, the coating composition may comprise the polymer-encapsulated opacifying pigment particles described in International Patent Publication No. 2007 / 112503A1.

Example

The following examples are for illustrative purposes only and are not intended to limit the scope of the invention.

Intermediate 1

Dibenzylamine (7627 g) was charged to a 24-LN ₂ -purified pressure vessel. After pressurizing the reactor, and several times with N ₂ exhaust, with N ₂ And then heated to 130 캜. Ethylene oxide (1880 g) was fed to the reactor at a rate such that the pressure was maintained below 60 psia (about 4 hours). After the addition of ethylene oxide, the reaction mixture was stirred at 130 DEG C for 14 hours. After lowering the temperature to 60 ° C and releasing the pressure, 45% potassium hydroxide (70 g) was added to the vessel and the reaction mixture was stirred at 110 ° C to remove water. The temperature was raised to 130 캜 and butylene oxide (11,277 g) was fed to the reactor at a rate such that the pressure was maintained below 60 psia (about 31 hours). Upon completion of the addition, the reaction mixture was stirred at 130 캜 for 4 hours. The reaction mixture was cooled to room temperature and the reaction mixture was neutralized with acetic acid.

Intermediate 2

Bis (2-ethylhexyl) amine (2010.0 g) was heated to 110 DEG C under a nitrogen atmosphere in a round bottom flask equipped with a condenser, an addition funnel and a mechanical stirrer. Glycidol (685 g) was added dropwise to the reactor over 2 hours with vigorous stirring. After the addition of glycidol, stirring was continued for 1 hour. The product was purified by vacuum distillation (165-175 DEG C; 1.0 mm Hg).

Intermediate 3

Diamylamine (372.4 g), butyl glycidyl ether (346.2 g) and water (27 g) were heated to reflux temperature (105-115 ° C) under a nitrogen atmosphere in a round bottom flask equipped with a condenser and mechanical stirrer. After 5 hours, the mixture was cooled to 30 < 0 > C. The product was isolated after removal of water and residual butyl glycidyl ether through vacuum distillation (14 mm Hg) at 30-150 ° C temperature range.

Example 1 - Preparation of HEUR Polymer Based on Intermediate 1

CARBOWAX ^TM 8000 polyethylene glycol (trademark of Dow Chemical Company or its affiliates, molecular weight = 8200; 1539.1 g) was heated to 110 ° C under vacuum in a batch melt reactor for 2 hours. Butylated hydroxyl toluene (BHT, 0.191 g) was added and mixed for 5 minutes. Then, Desmodur WH ₁₂ -MDI (108.19 g) was added to the reactor and mixed for 5 minutes. Thereafter, a solution of bismuth octoate (28%, 3.85 g) was added to the reactor and the mixture temperature was maintained at 110 DEG C with stirring for 10 minutes. Then, Intermediate 1 (258.16 g) was added to the reactor and the temperature was maintained at 110 캜 with stirring for 10 minutes. The resulting molten polymer was removed from the reactor and allowed to cool.

Comparative Example 1 - Preparation of HEUR Polymer Based on Bis (2-ethylhexyl) aminoethanol

CARBOWAX ^TM 8000 polyethylene glycol (molecular weight 8200; 1709.8 g) was heated to 110 ° C under vacuum in a batch melt reactor for 2 hours. The reaction mixture was then cooled to 85 캜 and then bis (2-ethylhexyl) aminoethanol (91.58 g) was added and stirring was continued for 5 minutes. IPDI (78.44 g) was then added to the reactor and mixing continued for 5 minutes. A bismuth octoate solution (28%, 4.27 g) was then added to the reactor. The mixture was then maintained at 85 DEG C with stirring for 20 minutes. The resulting molten polymer was removed from the reactor and allowed to cool.

Comparative Example 2 - Preparation of HEUR Polymer Based on Bis (2-ethylhexyl) aminoethanol

CARBOWAX ^TM 8000 polyethylene glycol (molecular weight 8200; 1844.0 g) was heated in a batch melt reactor to 110 ° C under vacuum for 2 hours. Intermediate 2 (31.54 g) and Intermediate 3 (19.74 g) were added to the reactor and allowed to mix for 5 minutes. IPDI (76.38 g) was then added to the reactor and mixing continued for 5 minutes. A bismuth octoate solution (28%, 4.40 g) was then added to the reactor. The mixture was then held at 110 DEG C with stirring for 12 minutes. The resulting molten polymer was removed from the reactor and allowed to cool.

Study on thermal aging stability

The thermal aging stability of the extended paint was evaluated in a satin white formulation with a pigment volume concentration of 40.5% by volume and a total solid concentration of 38.0% by volume. The formulation comprises 30.3 wt% of a wet ROVACE ^TM 661 vinyl acrylic binder (trademark of Dow Chemical Company or an affiliate thereof) based on the weight of the wet paint formulation, and 4.1 wt% of wet RHOPLEX based on the weight of the wet paint formulation ^TM SG-10M acrylic copolymer (trademark of Dow Chemical Company or one of its affiliates). Paint comprising a poly (vinyl acetate) binder having an initial pH of about 9 is known to decrease in pH as it ages due to hydrolysis of the acetate group. The initial paint pH of about 9 can improve the colloidal and biocide stability of the paint. The paint pH typically decreases to about pH = 7 with aging, resulting in a drastic slowing of the hydrolysis rate. Thermal aging is typically used in laboratory studies to accelerate the effects of paint aging. It is not desirable that the viscosity is greatly reduced with aging. Table 1 shows the results of a heat aging stability study.

Thickener Usage Level (%) pH1 Stormer
(Stormer) 1 pH2 Stormer 2 ? Stormer Example 1 0.32 9.0 99 8.8 102 +3 Comparative Example 1 0.51 9.1 95 8.1 73 -22 Comparative Example 2 0.40 9.0 111 8.2 81 -30 SCT-275 0.41 9.0 109 8.1 96 -12

The level of use (%) is the concentration of the thickener used in the paint. The concentration is expressed as a weight percentage of the dry active thickener relative to the wet weight of the final paint. Thickener of Examples 1-3 and Comparative Examples Thickener was added as a 16 wt.% Active thickener aqueous dispersion. These aqueous thickener dispersions also contained lactic acid in a wet weight percent of 3 supplied. Lactic acid was fed to 85% solids. The thickener dispersions were prepared by combining dry thickener solids, water and lactic acid in a sealed plastic 50 mL centrifuge tube, and slowly rotating the mixture for 2 days to thoroughly homogenize the thickener solids.

pH 1 is the initial pH of the paint measured at 1 hour after formulation of each paint. The pH was adjusted to the indicated value using ammonia.

Stormer 1 is the initial stomer viscosity of the Krebs Unit of the paint measured at 25 占 폚 in a 1/2-point metal can. Storm 1 was measured 24 hours after the paint formulation. During this equilibration period, the paint was maintained at 25 占 폚. Immediately prior to measuring the Stormer viscosity, the paint was poured into a 1/2-pint metal can and stirred for 20 seconds with a tongue depressor. The Kreb Viscometer is a rotating paddle viscometer according to ASTM-D562. KU viscosity was measured on a Brookfield Kreb unit viscometer KU-1 + available from Brookfield Engineering Lab (Middleboro, MA, USA).

pH 2 is the pH of the paint after storage for 2 weeks in a 60 ° C oven. During the heat aging process, the paint was stored in a sealed metal can.

Stormer 2 is the final Stormer viscosity in creep per unit of thermally aged paint measured at 25 占 폚 in a 1/2-point metal can. Immediately prior to measuring the Stormer viscosity, the paint was vigorously agitated with a pressure gauge for 20 seconds.

The ΔStormer of the creep unit is the same as that of Stormor 2 minus Stormer 1. A? STOMER numerical value closer to zero is preferable.

SCT-275 refers to ACRYSOL ^TM SCT-275 flow control agent (trademark of Dow Chemical Company), a non-acid-inhibiting polyurethane-related thickener commercially available from The Dow Chemical Company. The as-obtained product viscosity is inhibited by the use of a butyl carbitol-water-solvent mixture.

The paint increased by the thickener of Example 1 is much less viscous with aging as compared to the paint increased by the comparative example. The decrease in viscosity with aging exhibited by the paint exhibited by Example 1 was similar to or better than that of the incremental paint using a commercial flow control agent wherein the commercial flow control agent is different from the thickener of the present invention in that the VOC .

Claims (5)

delete delete A composition comprising a stable aqueous dispersion of an alkylene oxide urethane polymer modified hydrophobically by endcapping tertiary amine groups, characterized by the structure:

In this formula,
Each R < ¹ > is independently methyl or ethyl;
n is 1 to 10; delete delete